Inorganic polymers



United States Patent 3,373,001 INORGANIC POLYMERS William C. Drinkard,Jr., Wilmington, Del., assignor to E. I. du Pont de Nemonrs and Company,Wilmington, Del., a corporation of Delaware No Drawing. Filed Dec. 18,1963, Ser. No. 331,379 16 Claims. (Cl. 23-358) ABSTRACT OF THEDISCLOSURE New B boron-cage radicals and wholly inorganic polymerscontaining these B boron-cage radicals and a process for theirmanufacture. The process comprises reacting a lower oxide of a Group V,VI, or VII element in a solution of (H O) B H at a temperature of 0 C.to 50 C.

This invention concerns polymers containing B boroncage radicals andmore particularly to wholly inorganic polymers containing B boron-cages.

The term boron cage refers to the ten boron atoms which are present inthe repeating units of the polymers of this invention and which aredeemed to be joined to form a skeleton-like unit or cage in which eachboron atom is adjacent to at least four other boron atoms. The manner inwhich the boron atoms are linked is not known but the group of which theten boron atoms are a part functions as a unit in chemical reactions.

There has been considerable interest during recent years in boronchemistry and particularly in boron compounds containing relativelylarge proportions of boron. Some of these are disclosed in applicantspending applications S.-N. 220,909, filed Aug. 31, 1962, now abandoned;S.-N. 220,910, filed Aug. 31, 1962; and SN. 240,755, filed Nov. 28,1962, but heretofore polymers containing only inorganic constituents andB boron-cages in the skeletal chain have not been known. In accordancewith this invention there are provided novel polymers characterized bywholly inorganic backbones containing at least two B boron-cage radicalsin combination with one or more elements having an atomic number of atleast and from Groups V, VI and VII of the Periodic Table of Elements(Hackhs Chemical Dictionary, 3rd ed. (1950) The backbones of thepolymers are free from carbon atoms. Organic and/ or inorganicsubstitutents can be attached to backbones of these polymers but neitheris necessary.

Polymers of this invention are characterized by the following structuralunits, including combinations thereof:

where M is a cation,

X is a group which can be bonded to a nuclear carbon of an aromatic ringhaving benzenoid unsaturation by replacement of hydrogen,

Q is

Se, -'re or mixtures thereof,

b is a positive whole number from 0 to 8, inclusive,

b is a positive whole number from 0 to 9, inclusive,

3,373,001 Patented Mar. 12, 1068 a and h are positive whole numberswhose values are determined by the valence (v of M and the valence (v ofthe bracketed unit,

c, d and e are whole numbers, greater than zero, referring to the numberof parenthetical units in the compound, R is a monovalent hydrocarbonradical.

When X or R is or contains an organic radical, it may contain from 1 to30 or more carbon atoms but preferably it contains 17 carbon atoms andis phenyl or a lower alkyl group (less than 8 carbon atoms). The termcation refers to an atom or group of atoms which forms a positivelycharged ion in aqueous solution. The term hydrocarbon radical refers toa radical of carbon and hydrogen, generally, of which alkyl, aryl,aralkyl, alkaryl and alicyclic radicals are particularly preferredspecies.

The values of c, d and 2 may range from one in the case of linear dimersto large whole numbers for polymers of the order of 32,000 molecularweight or more. The latter are usually gels and are normally insolublein ordinary sovents other than dimethyl formamide, dimethyl acetamide,etc. Molecular weights of the products are generally governed by themole ratio of the reactants used. For example, reaction of (H O) B Hmwith SeO is a mole ratio of 1:1 produces a gel with high molecularweight having the formula (B H Se-3H O-h, where n is a large wholenumber, but if only /2 mole SeO is used, the product is the dimer [B HseB l-l F, recoverable as a cesium salt Cs [B H SeB H Similarly,reaction of As O with (H O) B ,H in ratios less than 1:2 has producedthe dimer ion which is also recoverable as the cesium salt.

The oxides of other Group V, VI and VII elements mentioned above canlikewise be utilized to produce similar polymers containing sulfur,antimony, tellurium, bismuth, phosphorus and halogens such as bromineand iodine, and combinations thereof.

Also, these polymers can be further reacted to attach substituents tothe boron cages in the polymer as, for example, by halogenation. All, orless than all, of the hydrogen atoms in the boron-cage structure in thepolymers can be replaced with halogens (Cl, Br, I or F). Also, reactionof one mole HB H -DMF with one-half mole Se0 in water produces the dimerEvaporation of the solution produces a glass. Similarly, by substitutingthe other oxides mentioned above, for 8e0 inorganic dimers of the GroupV, VI and VII elements mentioned are attained having DMF terminalgroups.

The polymers of this invention are prepared by reacting the B H ion witha lower oxide of an element of one of the Group V, VI and VII elementsmentioned above. Such a lower oxide is an oxide of one of these elementsin which the latter exhibits a valence less than its maximum permissiblevalence state (eg, less than 5 for Group V Elements, less than 6 forGroup VI and less than 7 for Group VII). The reaction is carried out inan acidic solution (having a pH less than about 7) of the B H ion.Preferably the reaction medium is fairly strongly acidic and has a pH ofless than 2 because of the need for the B H ion to be in the form of itshydronium salt (H O) B H A convenient method of operation involvesdissolving a salt such as (NHQ B H or Na B H in water or other suitablesolvent, adding a lower oxide of a a Group V, VI or VII element andacidifying by bubbling HCl gas through the reaction mixture or byaddition of another acid such as HBr, H SO H PO toluene sulfonic acid,acetic acid, trifiuoroacetic acid or the like. If desired, the B H ioncan be used in its acidic form H B H in which case no additional acidneed be used.

Preferred oxides for carrying out the process of this invention arelower oxides or substituted oxides of sulfur, selenium, tellurium,arsenic, antimony, bismuth, phosphorus and iodine. These areconveniently used in the form of S 5e0 TeO As O Sb O RAs\ Bi O P 0 R andH10 respectively, or their solvates (H 80 H SeO As(OH) etc.) Where R isa. monovalent hydrocarbon radical, but other forms can be used. Theparent oxides useful in this invention contain at least one unit of thefollowing generic structure:

Electron pairs Oxide p 'm n bonding O to Y O 3 0 0 3 0 0 3 0 3 0 0 2 0 03 2 1 0 3 2 0 l 3 3 0 0 3 3 0 0 3 3 O 0 3 2 O 0 3 2 0 0 3 R-As As-R 2 12 0 ?H R- S :0 1 1 1 1 H s 0 3 1 2 U 1 The reaction of this invention iscarried out in a solution of the B H ion in a suitable innocuous solventsuch as water, dimethyl formamide, dimethyl acetamide, an alcohol,acetonitrile, N-rnethyl pyrrolidone and the like. The solvent is notcritical and any innocuous liquid which dissolves the boron compound canbe used. Sometimes the oxide reagent is not soluble in the solvent andthe reaction is a two phase reaction.

The reaction of this invention is exothermic and can be conducted atnormal room temperature and lower (even at 0 C. in some instances) butslight warming above room temperature is sometimes desirable to shortenthe reaction time. With certain oxides cooling may be necessary toprevent overheating. Usually temperatures above about 100 C. areunnecessary and the boiling point of the reaction solution should not beexceeded. Completion of the reaction is indicated by gel formation orincreasing viscosity of the reaction solution when the product is a highmolecular weight polymer. When low molecular weight polymers areprepared, completion of the reaction is usually indicated by a change incolor of the solution. In any event disappearance of the oxide reagentsignifies that reaction is completed.

In Formulas 1 and 2 above, the component represented by X is defined as.a group capable of bonding to a ring carbon of an aromatic ring by areplacement of hydrogen. An aromatic ring is defined as one possessingbenzenoid unsaturation (e.g., as in benzene, naphthalene, xylene, etc.)The group X is preferably a halogen or a monovalent group bonded toboron in the B cage through nitrogen, carbon, oxygen or sulfur as, forexample, in the following groups: amino, substituted amino, nitroso,nitro, azo, alkyl, alkenyl, alkynyl, aryl, alkaryl and aralkyl, cyano,carboxyl, hydroxy, hydrocarbonyloxy, hydrocarbyloxy, thiol,hydrocarbylrnercapto, sulfo, sulfonyl and sulfamyl.

The group X can be a substituent on the boron cage prior topolymerization or can be introduced into the polymers of this inventionby direct reaction with those polymers or by substitution for ormodification of a group which has been introduced into the polymer bydirect reaction (e.g., a substituent obtained by reduction,esterification, hydrolysis, dehydration, or amidation of directlyintroduced groups). Substituents which are introduced by direct reactionare preferred. Thus, X may be a mixture of the above groups.

Examples of groups included within the scope of X are as follows:halogens (F, Cl, Br, I), hydrocarbon, carboxyl carbamyl andN-substituted carbamyl where Y is F, Cl, Br, I, halomethyl (CH Y', whereY is F, Cl, Br, 1), hydroxy (OH), hydrocarbyloxy (OR'), acetal [-CH(OR')ketal [CR(OR) hydrocarbylcarbonyloxy [OC(O)R'], hydrocarbyloxycarbonyl[-C(O)OR'], isocyanate (NCO), thiocyanate (CNS), isothiocyanate (NCS),hydrocarbylthio (-SR'), hydroxymethyl (CH OI-I), hydrocarbyloxymethyl(CH OR'), dihydrocarbylaminomethyl (CH NR' cyano (--CN), amino (NHsubstituted amino (NHR', -NR trihalomethyl (--CCl CF13, etc.)

nitro (NO nitroso (NO), azo (N=NAr, where Ar is an aromatic hydrocarbonof up to 10 carbons), sulfo (-SO H), sulfonyl (-SO R'), andacetoxymercury R, where used in the above substituents, is a monovalentorganic group which is preferably a hydrocarbon group (alkyl,cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl, aralkyl, and the like)of at most 18 carbons.

Examples of reagents which are within the scope of the above definitionand which are operable in the process of the invention are given below,together with the substituent group which in the process is bonded toboron in the final product.

Reagent Group Bonded to Boron Halogens (F Ch, Bra, In) Halogen (F, Cl,Br, I)

Nitric acid -Ni HzNOSOaNa NH Olefins alkyl [e.g., CiH5, CH(OH3);1

Alkyl halides alkyl 0 Acyl halides ('.'.R

(CN)2C=C(CN)z (CN)C=C(CN):

COClg O CO/HCI --('?[H O CoHsN(CHs)CHO/POCl l JH 13. 80201 SOz--R O R2N( Cl NR2 R gH and R 00 -OR (HsO)+Ol- (hydronium salt) OH R 801 SR Inthe above groups, R is a monovalent organic radical, preferablyhydrocarbon of at most 18 carbons, which can be alkyl, lkenyl,cycloal-kyl, cycloalkenyl, aryl, alkaryl, aralkyl and the like.

In the reactions employing the above reagents, a catalyst may be used,e.g., aluminum trichloride, boron trifiuoride and polyphosphoric acid.These catalysts are employed in the same manner as in the well-knownprocedures in organic chemistry. In some cases the boron compoundsthemselves function as catalysts, e. g., in alkylation of compounds ofthe formula H'(B1HQZ), The re agents [are materials which are usuallyreadily available or which are obtained by conventional methods.

Reaction of the boron compounds of Formulas 1 or 2 or a combinationthereof to replace hydrogens on the boron cages with substituent groupsis conducted in conventional vessels with corrosion-resistant innersurfaces, e.g., glass, platinum, poly(tetrafiuoroethylene)resin, and thelike. The boron-containing reactant, and optionally an inert liquidsolvent, is charged into the reaction vessel. The reactant containingthe group to replace hydrogen on the boron cage is then supplied to thereaction vessel at a temperature and at a rate which Will provide acontrollable reaction and which will bring the reaction to completionwithin a reasonable time. When reactants are employed which arehydrolytically stable, water or al cohols (methanol, ethanol) can beused conveniently as a medium for the reaction. Other solvents can beused, for example, diethyl ether, benzene, heptane, carbontetrachloride, carbon disulfide and the like.

The temperature at which the reaction is conducted Will be determinedlargely by the reactivity of the substituting reagent. In general, thetemperature will be between about 20 and 200 C. Preferably, thetemperature will be between about 0 and about 150 C.

The time of reaction in a batch process will also depend to aconsiderable extent on the reactivity of the reactants used. Thereaction generally proceeds rapidly and, with thorough mixing of thereactants, the time may be as low as 5 minutes or even less. Generally areaction time between about minutes and 5 hours is sufiicient. It isdesirable and advantageous to mix the reactants by any suitable meansalthough mixing is not essential for operability.

The reaction can be conducted under pressure, if desired, but is notessential to use pressure. In most cases the reaction proceedssatisfactorily at atmospheric pressure.

The proportions in which the reactants are used are not critical. It ispreferable, in order to obtain maximum yield of desired product, to useat least one mole of the substituting reactant for each hydrogen whichis to be replaced on the boron-containing reactant. It is not essential,however, that these ratios be used.

Compounds of Formula 2 are preferred for practical utility as being morestable than the linear polymers of Formula 1. The molecular Weights ofboth the linear polymers and the cross-linked polymers of Formula 2 mayrange from that of the dimers to more than 30,000. The cross-linkedpolymers are particularly suitable for preparing articles ofpredetermined shape as by molding, forming unsupported films and thelike. Sulfur containing B cage inorganic polymers possess antistaticproperties.

Halogenation of the polymers of this invention to replace hydrogen atomson the boron cages with halogen atoms can be conducted very simply aftersuspending the B compound in water. The desired halogen is admixed withthe solution at room temperature. Sometimes heating is necessary if alarge number of halogens are to be substituted on each cage. Thereaction is exothermic and its completion is usually signified by atemperature decline and/ or by a color discharge. As many as eighthalogens can be substituted on each B cage in the polymer; nine halogenson the terminal groups.

The exact structural formula for the cross-linked polymers of thisinvention has been carefully investigated and all available evidencepoints to a structure of Formula 2 above inwhich Qs are connected by a.cross-linking oxygen group.

When b and b in Formulas 1 and 2 are zero, the polymers have the simpleformulas:

" B 10Ha-Se L Jo mHsS T Jo l ,l LB iuHsT JG phenyl phenyl J: l c L lo sSJ phenyl phenyl BieHs- I phenyl phenyl Bm sSb phenyl I Hi3 ioHaSb io al HB1uHaBi BinHr h PREPARATION OF (NHQ B H A reaction vessel having acapacity of about 365 parts of water is charged with 0.79 part ofdecaborane ('14), cooled in liquid nitrogen, and then evacuated to apressure of microns of mercury. Approximately 21 parts of methyl sulfideis condensed onto the decaborane in the reaction vessel. The reactionvessel is closed, allowed BmHo B iuHo to warm to room temperature (about25 C.) and stand for 4 days. During this period, 6.6 millimoles ofhydrogen is evolved. The reaction vessel is opened and excess methylsulfide is removed by distillation, leaving a practically quantitativeyield of white solid residue of B H -:2S(OH The compound isrecrystallized from ethyl acetate and it melts at 122-l-24 C. Thecompound is called bis(dimethylsulfide)decaborane.(l2).

.Bis(dimethylsulfide)decaborane(l2) (8.5 g.) is mixed with 50milliliters of liquid ammonia and stirred in a round-bottom reactionvessel for one hour with the vessel being cooled to a temperature ofabout -50 C. by partial immersion in a mixture of solid carbon dioxideand acetone. The cooling bath is then removed and the excess ammonia isallowed to evaporate with stirring. The remaining traces of ammonia areremoved by subjecting the residue to a high vacuum (0.01 mm. of mercury)at 25 C. There is obtained 5.6 g. of solid residue which is virtually aquantitative yield of diammonium decahydrodecaborate(2-), i.e., (1N-H BH The invention will be more clearly understood by referring to theexamples which follow. All parts are by weight unless otherwiseindicated.

Example 1 [Bmligsfi 311201 A solution of 15.4 g. of (NHQ B H dissolvedin 20 ml. of water is passed through an Amber-lite lR- -H ion exchangecolumn to produce the acid, (H O) B H A solution of 10.8 g. of $602 in30 ml. of water is added and the solution stirred well. The solutiongradually darkens to a deep red-brown color and after approximately 20minutes it sets to a firm red-brown gel. The product is purified bywashing with water. It is dried in a nitrogen atmosphere.

Analysis.--Calcd. for [B H Se-3H O] Se, 31.7; H, 5.6. Found: Se, 31.6;H, 5.3. End group titration indicates that 11:21. The gel is insolublein all solvents tried. However, dilute solutions of the polymer areprepared by the reaction Of S502 and HzBmHm il'l Other solvents may beused for polymer formation, for example, ethanol and other nonbasicsolvents which dissolve salts or the acid form of the B H ion.

(NHQ B H can be used directly by addition of I-ICl to the solution.

Example 2 A solution of 1.0 g. of Cs [B H SeB H in 20 ml. of warm wateris passed through an Amberlite IRl20 H ion exchange column to producethe acid,

The solution is evaporated in vacuum at 25 C. to give a gummy residue.The residue is suspended in 20 ml. of glyme and six drops of propyleneoxide are added. The temperature rises rapidly to approximately 32 C.The reaction mixture is allowed to stir for one hour and then the glymeis evaporated in vacuum at 25 C. The residue is dissolved in a mixtureof 20 ml. of ethanol and 20 m1. of water and the product precipitated asa yellow solid by the addition of a solution of CsF in ethanol. Productis recovered by centrifugation and purified by washing with ethanol.

Analysis.--Calcd. for Cs [B H SeB H (OC H C, 5.66; H, 3.76. Found: C,6.42; H, 3.79.

That the propyloxy group is attached directly to the boron cage isconfirmed by the infrared spectrum of the product showing a B--O bond.

A solution of 7.7 g. of (NH hB l-l in 20 ml. of Water is passed throughan Amberlite 1R120H ion exchange column to produce the acid (H O') B H Asolution of 2.7 g. of Se in 25 ml. of water is added dropwise to thesolution of (H O) B H The solution immediately becomes dark red-brown incolor. The product is recovered by the addition of an aqueous solutionof 15.0 g. of CsF. Cs [B H SeB H precipitates as a light browngelatinous solid which may be purified by recrystallization from water.

Analysis.-CalCd. for CS [B H SeB H ]Z Se, 13.6; Cs, 46.0; H, 3.11.Found: Se, 14.07; Cs, 48.4; H, 2.54.

The equivalent weight of the product is found to be 285. Theoreticalequivalent for Cs [B H SeB H is 287. The structure of the product isfurther supported by IR, UV and NMR spectra. Conductivity measurementsshow that the anion has a valence of two.

A solution of 7.2 g. of (NH B H is dissolved in 20 ml. of water and thesolution is passed through an Amberlite IR-120H ion exchange column toproduce the acid, (H O) B H A solution of 4.13 g. of SeO in 20 ml. ofWater is added dropwise to the solution of (H O) B H The solutionbecomes dark red-brown in color. Product is precipitated as a dark tancolored solid by the addition of 15.0 g. of CsF dissolved in 25 ml. ofwater. The product is insoluble in hot water. It is purified by repeatedwashings with water.

Analysis.-Calcd. for CS2[B1QH9SB1QHSB1QHQ]I SC, 20.2; Cs, 34.4; H, 3.36.Found: Se, 20.37; Cs, 35.9; H, 3.60.

Example 5 A solution of 1.0 g. of Cs [B I-I Sel3 H in ml. of water ispassed through an Amberlite IR120'-H ion exchange column. The acidsolution which results is evaporated to dryness in vacuum at C. Thered-brown residue is dried in vacuum over P 0 for minutes at 25 C.

Analysis.-Calcd. for 22.48. Found: Se, 23.2.1.

The acid, which is a solid, is a strong acid. Both protons titratetogether with NaOH) A solution of 10.0 g. of Cs[B H -DMF] in 100 ml. ofwater is passed through an Amberlite IR-lZO-H ion exchange column toproduce the acid A solution of 1.72 g. of SeO in 10 ml. of water isadded dropwise to the (H 0) [B H -DMF] solution. The solutionimmediately becomes deep redbrown but no solid forms. Water is removedfrom the solution by evaporation in a stream of air. A red-brown glassresults. The glass is dissolved in 20 ml. of 10% KOH and the solution isheated at 50-60 C. in a stream of N until the odor of HN(CH is no longerpresent. The solution is cooled to 25 C. and the product is precipitatedby the addition of an aqueous solution of CsF. The solid is recovered bycentrifugation and washed with ethanol.

Analysis.Calcd. for CS [(HO)B H SeB H (OI-I)]1 Cs, 43.52; Se, 12.92.Found: Cs, 45.7; Se, 12.27.

An infrared spectrum shows that the hydroxyl groups are attacheddirectly to the boron cage.

Chlorine gas is bubbled into a suspension of 1.0 g. of Cs [B H SeB H in20 ml. of water. The temperature rises gradually to approximately 70 C.and the solid dissolves. Chlorine gas is bubbled into the solution for30 minutes. At the end of this time the temperature has 10 dropped toapproximately 40 C. The solution is then cooled to 25 C. and the productis precipitated by the addition of [(CH N]Cl. The brown gelatinousproduct is recovered by centrifugation and purified by repeatedlywashing with water (six times).

Analysis.-Calcd. for

N, 3.8; Se, 11.7; CI, 38.5. Found: N, 3.4; Se, 11.99; CI, 41.1.

A solution of 7.2 g. of (NH B H in 20 ml. of water is passed through anAmberlite IR-- ion exchange column to produce the acid (H O) B H Asolution of 2.7 g. of Se0 in 25 ml. of water is added dropwise to the (HO) B H solution. The solution becomes deep redbrown in color. ElementalBr is then added dropwise to the solution. A sharp rise in temperatureis noted and the temperature is maintained at approximately 50 C. bycooling during the addition of Br When 57 g. of Bl'g is added there isno evidence of heat evolution and Br; vapor is present above thesolution. Excess Br is removed by bubbling N through the solution.Product is precipitated as a yellow-orange solid by the addition of 15.0g. of CsF dissolved in 20 ml. of water. The product is purified bywashing with water.

Analysis.-Calcd. for Cs [B H Br SeB H Br Se, 5.61; Br, 57.86. Found: Se,5.5; Br, 55.7.

Example 9 2[ io s.5 2.5 10 e.5 2.5]

An aqueous solution of I KI is added dropwise to a solution of 1.0 g. ofCs [B H SeB H in 10 ml. of water. The reaction mixture is maintained at50 C. during the addition of 1 Addition is continued until the color ofI persists. The solution is then cooled to 25 C. The product separatesas an orange-yellow solid.

Analysis.-Calcd. for CS [B H I SeB H I Se, 6.55; I, 52.5. Found: Se,6.64; I, 54.74.

Example 10 m uASBm n l CS4[ O BmHgASBmHg A solution of 15.4 g. of (NI-lB I-l dissolved in a minimum amount of water is passed through anAmberlite IRl20H ion exchange column to produce the acid, (H O) B HApproximately m1. of eluent is collected. To this solution is added 4.92g. of As 0 and the mixture is heated at 60 C. until the arsenic trioxidedissolves. This process requires 3-4 hours. At the end of this time ayellow-orange solution forms. The small amount of solid which is presentis removed by filtration, and the product is precipitated from thefiltrate by the addition of 30 g. of CsF dissolved in water. The mixtureis cooled in ice and filtered. The product is recrystallized from hotwater.

Analysis.-Calcd. for

0, 0.77. Calculated equivalent weight: 287. Found: 282, 287, 282.

Example 11 BIIJHDAS BioHo (H3 0): A

luHoAS BmH is dried in vacuum over P at 25 C. for 40 minutes.

Analysis.-Calcd. for

io v m n (I-I O) l: (I) l:

B H ASB HQ As, 21.6. Found: As, 22.07.

Example 12 A solution of Br in aqueous KBr is added dropwise to a hotaqueous solution of 1 g. of

B m Qfi B 0 CS4 B ro tASB 10119 (10 ml.) Addition of Br is continueduntil the color of the Br persists for five minutes. The solution iscooled to 0 C., and the product is recovered as a white solid when (C HNCl is added to the cold solution. The product is recovered bycentrifugation and purified by repeatedly washing with water.

Analysis.-Calcd. for

C, 12.7; H, 3.0; N, 1.85; Br, 63.2; As, 4.94. Found: C, 11.03; H, 3.0;N, 1.78; Br, 60.38; As, 4.05.

Example 13 BitI a.5h.5ASB10Hs.5I2.5 CS4[ (I) ro e.s m w usIu A solutionof 1 in aqueous KI is added dropwise to a hot aqueous solution of l g.of

filtration and washed with water, ethanol and ether.

Analysis.Calcd. for

lll tl.5I2.51? l0 6.5 2.5 CS4; (I) I BioHa.5I2.a mHo.5Iz.s

I, 52.7; B, 17.9. Found: I, 51.72; B, 16.73.

Example 14 B m nAS mHs CS4 (I) BmHpAS B roHw in ml. of water is passedthrough an Amberlite IR- 120-H ion exchange column to produce the acidThe solution is evaporated in vacuum at C. to give a light yellow oil.The oil is suspended in 20 ml. of glyme (ethylene glycol dimethylether), and six drops of propylene oxide are added. A dark red-brown gumresults. Addition of 10 ml. of water to the mixtures causes the gum ofdissolve to give an orange solution. A solution of CsF in ethanol isadded until precipitation of the gelatinous product is complete. Productis recovered by centrifugation and purified by washing with water,ethanol and ether.

Analysis.-Ca1cd. for

BmHuiXSBmHK C3137) CS4[ :12

EwHnASBmHs O Ca 7) C, 5.67; H, 3.80. Found: C, 5.47; H, 3.77.

That the propyloxy group is attached directly to the boron case isconfirmed by the infrared spectrum of the product.

Example 15 Solid As O (0.98) is suspended in a solution of 1.54 g. of(NHQ B H in 75 ml. of dimethyl formamide. Then HCl gas is bubbled intothe mixture for six minutes. During this time, the solution becomes hot,the As O dissolves to give a yellow solution and there is a noticeableincrease in the viscosity of the solution. The polymer remains insolution in DMF, but it may be recovered as a light yellow solid byadding the DMF solution to water. The polymer has the formula [B H As]Molecular weight by light scattering equals 32,400.

Example 16 A solution of 0.73 g. of Sb O in 10 ml. of concentrated I-IClis added to a solution of 7.7 g. of (NHQ B H in ml. of water. Thesolution is then heated at C. for one hour. During this time, thesolution becomes redbrown in color. The solution is cooled to 25 C., andthe product is precipitated by the addition of 15.0 g. of CsF dissolvedin a minimum amount of water. The orange-brown solid is purified byrecrystallization from water and identified as A solution of 7.7 g. of(NHQ B H is passed through an Amberlite IR-l20-H" ion exchange column toproduce the acid (H O) B H To this solution is added 2.46 g. of solid AsO and the mixture is warmed at 50-60" C. until the solid has dissolved.A solution of 2.7 g. of SeO in 25 ml. of water is then added and themixture allowed to stand. Within fifteen minutes the solution sets to abrown gel. Attempts to recover the gel after washing with water areunsuccessful. The material disperses and cannot be recovered bycentrifugation. Addition of an aqueous solution of 3.7 g. of CsF causesthe gel to lighten in color, and it is then possible to centrifuge thegel for recovery. The solid is purified by Washing with water andidentified as m B FS mHsSe C S2.- (I) 1; unitsa mse Yield is 10.7 g.

Analysis.Calcd. for

m s l mHaSe CS2n[ (I) BmHgASBwHsSB x: As, 14.00; Se, 14.75. Found: As,13.24; Se, 14.72.

Example 18 B IIJ D IU B lO B lD B Solid C I-1 (2.36 g.) is sprinkledinto a well stirred solution of 3.08 g. of (NI-LQ B H in 30 ml. ofwater. The temperature rises to 35 C. and a grey gum forms in a clearcolorless solution. Liquid is removed by decantation and a concentratedsolution of 6.0 g. of CsF in water added. A white solid formsimmediately. Solid product is recovered by filtration and recrystallizedfrom hot water. It is identified as I l ic tl w a m aIB 10H Calculated:Cs, 33.0; C, 13.4; H, 3.04; I, 28.8. Found: Cs, 33.0; C, 12.61; H, 3.17;I, 24.14.

Example 19 The product is BwHgAS-ZHzO l l l B10Ha1lS-2H2O uAnalysis.-Calcd. for

m mas-21:20 l l l BwHgJlS-2H2O 1:

As, 33.0. Found: As, 33.89; 32.93.

Example 20 t OsrIBroHvIBwHiIBmHvMHzO A solution of 5.91 g. of NalO in 60ml. of water is added dropwise to a Well stirred solution of 9.24 g. of(NI-I B H and ml. of concentrated HCl in 30 ml. of water. When additionis complete the reaction is a light yellow solution containing a smallamount of White solid. Solid is removed by filtration and 18 g. of CsFin Water is added. A yellow solid forms immediately and is recovered byfiltration and recrystallized from hot water. It is identified asCalculated: Cs, 42.8; B, 26.0; I, 20.1. Found: Cs, 42.6; B, 26.03; I,20.47.

1 4 Example 21 BmHnASBmHgASBmHn iuHn SBwHM SBwH A solution of 7.7 g.(0.05 mole) of (NH B H was passed through an Amberlite IR120-H ionexchange column to give the acid (H O) B H To the solution was added2.46 g. (0.025 mole) of A5203 and the mixture was warmed at 50-60 C.until all of the As O had dissolved. Addition of aqueous CsF to theyellow solution resulted in the precipitation of crude product.Fractional crystallization from water gave a product which correspondsto the formula B mH JIXS BwHgAS B 0119 CS4 B mIIpASBlOHEAS mHt' Example22 Yield was 2.9 g.

Fractional crystallization of a product prepared according to theprocedure of Example 20 resulted in an isolation of a more highlypolymerized species.

Analysis.-Calcd. for

l l I I CSdBmI-IpI m sIBmHsI m sI 10 0]: Cs, 40.8; B, 27.6; I, 26.0.Found: Cs, 41.1; B, 26.71; I, 26.35.

Example 23 A solution of 15.4 g. (0.01 mole) of (NHQ B H and 10.8 g.(0.1 mole) of NaHSO in 125 ml. of water Was treated with 43 ml. ofconcentrated HCl. Within 15 minutes the yellow solution sets to a lightamber gel. The product was washed with water in a Waring Blendor andrecovered by centrifugation. Water was removed in vacuum at 25 C. andfinal drying was accomplished in vacuum over P 0 Yield was 14.6 g.,

Example 24 BroHn (AS B HQMXSBmHQ (NH4) 8 (I) O IU Q 1011 (QLSB wHgExample 25 BwHalikSBwHsS C5211 (I) v wHe s ioHeS n An aqueous solutionof 7.7 g. (0.05 mole) of (NHQ B H was passed through an Amberlite IR- -Hion exchange column to produce the acid (H O) B H A solution of 2.7 g.(0.025 mole) of NaHSO was added, and the solution was allowed to standfor 30 minutes. At the end of this time 2.46 g. (0.025 mole) of As O in30 ml. of concentrated HCl was added and the reaction was allowed tostand overnight. A deep amber color developed, but no gel formed.Product was recovered by the addition of a solution of 15.0 g. of CsF.Yield was 11.5 g.

Example 26 m s m a n A solution of 7.7 g. (9.05 mole) of (NHQ B H waspassed through an Amberlite 1R120-H ion exchange column to produce theacid (H O) B H To this solution was added a solution of 2.7 g. (0.025mole) of NaHSO and the reaction was allowed to stand for 30 minutes.Then :a solutiton of 2.7 g. (0.025 mole) of Se0 in 20 ml. of water wasadded and the reaction allowed to stand overnight. No gel formed. Aproduct was precipitated by the addition of aqueous CsF. Yield was 15.7g.

The compounds of this invention are generally useful in the preparationof unsupported films, coating compositions or molded products andparticularly in applications where compositions containing a largeconcentration of boron per unit weight are desirable. They may also beused in pyrotechnics to provide the characteristic boron flame testcolor.

M in the formulas is a cation used to fulfill the valence of theboron-cage anion. Since M does not appear in the polymeric product, itis not critical and may be any of the following: hydrogen, ammonium ormono-, di-, or tri-substituted ammonium in which the substituents arehydrocarbyl of up to 12 carbons free of aliphatic unsaturation and inwhich at most only one such substituent is aryl. Preferably, allsubstituents are lower :alkyl groups.

We claim:

1. A compound characterized by -a recurring structural unit selectedfrom the group consisting of M is a cation selected from the groupconsisting of hydrogen, hydronium, ammonium, substituted ammonium,sodium and cesium,

X is a radical selected from the group consisting of halogen,hydrocarbon, carboxyl, carbamyl, N-substituted carbarnyl, halocarbonyl,halomethyl, hydroxy, hydrocarbyloxy, acetal, ketal,hydrocarbylcarbonyloxy, hydrocarbyloxycarbonyl, isocyanate, thiocyanate,isothiocyanate, hydrocarbylthio, hydroxymethyl, hydrocarbyloxymethyl,dihydrooarbylaminomethyl, cyano, amino, substituted amino,trihalomethyl, acyl, aldehyde, nitro, nitroso, azo, sulfo, sulfonyl,acetoxymercury and combinations thereof,

Q is

Iii OH R R R and mixtures thereof,

Q is a trivalent radical selected from the group of As,

Sb, Bi and mixtures thereof,

b is a positive whole number from O to 8, inclusive,

b is a positive whole number from 0 to 9, inclusive,

a and h are positive whole numbers whose values are determined by thevalence (VM) of M and the valence (v of bracketed unit such that (v (a)(v (h),

c, d and e are whole numbers, greater than Zero, re-

ferring to the number of the respective parenthetical units in thecompound,

R is a monovalent hydrocarbon radical.

'2. A compound of claim 1 characterized by the recurring structural unitwhere the letters have the same significance as in claim 1.

3. A compound of claim 2 having the formula where the letters have thesame significance as in claim 2.

4. A compound of claim 3 in which Q is an element from Group V of thePeriodic Table of Elements having an atomic number of at least 15.

5. A compound of claim 3 in which Q is an element from Group VI of thePeriodic Table of Elements having an atomic number of at least 15.

6. A compound of claim 3 in which Q is an element from Group VII of thePeriodis Table of Elements having an atomic number of at least 15.

7. A compound of claim 1 having the recurring structural unit Where thesymbols have the same significance as in claim 1.

8. A compound of claim 7 having the formula Where the symbols have thesame significance as in claim 7.

9. A compound of claim 8 in which Q is an element from Group V of thePeriodic Table of Elements having an atomic number of at least 15.

10. A process for preparing a polymer containing a B boron-cage in thebackbone thereof which comprises admixing with a solution containing (HO) B H at a temperature below the boiling point of the solution theoxide having the formula is a non-bonding electron pair attached to Ywhere Y is an element from Groups V, VI and VII of the Periodic Table ofElements having an atomic number of at least 15, k, p, m and n are smallwhole numbers representing the number of the respective parentheticalcomponents in the oxide,

k is 1,

p is a number 0-3, inclusive,

m is a number 03, inclusive,

n is a number 0-1, inclusive,

k+m+n+ (number of electron pairs bonding oxygen to Y)=4.

11. The process of claim 10 in which the lower oxide of a Group Velement, having number of at least 15.

12. The process of claim 10 in which the lower oxide of a Group VIelement, having number of at least 15.

13. The process of claim 10 in which the lower oxide of a Group VIIelement, having number of at least 15.

14. The process of claim 19 in which the temperature is in the range ofabout 050 C.

oxide is a an atomic oxide is a an atomic oxide is a an atomic 1 7 1 815. The process of claim 10 in which the oxide has and Y is a Group Velement, having an atomic number the formula of at least 15.

YO No references cited. and Y is a Group VI element, having an atomicnumber of at least 15. 5 OSCAR R. VERTIZ, Primary Examiner.

16. The process of claim 10 in which the oxide has MILTON WEISSMANExamineh the formula H. S. MILLER, Assistant Examiner. Y O

